WO2021051486A1 - Carbon nanotube thin film/composite material forming method and manufactured lightning protection structure - Google Patents

Carbon nanotube thin film/composite material forming method and manufactured lightning protection structure Download PDF

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Publication number
WO2021051486A1
WO2021051486A1 PCT/CN2019/114633 CN2019114633W WO2021051486A1 WO 2021051486 A1 WO2021051486 A1 WO 2021051486A1 CN 2019114633 W CN2019114633 W CN 2019114633W WO 2021051486 A1 WO2021051486 A1 WO 2021051486A1
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Prior art keywords
carbon nanotube
nanotube film
lightning protection
composite material
protection structure
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PCT/CN2019/114633
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French (fr)
Chinese (zh)
Inventor
刘亚男
高丽敏
冯荣欣
祖岩明
Original Assignee
中国商用飞机有限责任公司北京民用飞机技术研究中心
中国商用飞机有限责任公司
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Application filed by 中国商用飞机有限责任公司北京民用飞机技术研究中心, 中国商用飞机有限责任公司 filed Critical 中国商用飞机有限责任公司北京民用飞机技术研究中心
Priority to EP19945839.9A priority Critical patent/EP4032691A4/en
Publication of WO2021051486A1 publication Critical patent/WO2021051486A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
    • B29C70/443—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding and impregnating by vacuum or injection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/002—Agents changing electric characteristics
    • B29K2105/0023—Agents changing electric characteristics improving electric conduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3076—Aircrafts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2571/00—Protective equipment

Definitions

  • the invention belongs to the technical field of aircraft composite material lightning protection, and in particular relates to a carbon nanotube film/composite material forming method and a manufactured lightning protection structure.
  • the lightning protection measures for composite materials are mainly by adding conductive functional layers on the surface, including surface flame spraying aluminum coating, bonding metal mesh, and bonding aluminum foil.
  • the aluminum coating protection method is to prepare the aluminum coating protection layer by flame spraying on the composite material matrix, that is, the transfer film method, or the plasma electroplating method to prepare the aluminum coating.
  • the optimal thickness of the coating is 0.20 mm.
  • the resistivity of aluminum is 2.83 ⁇ 10 -8 ⁇ m, and its electrical conductivity is good. After the aluminum coating is sprayed on the surface of the composite material, a continuous conductive layer will be formed. This conductive layer is the electrostatic charge generated by the aircraft due to friction or induction And the strong current generated by lightning provides a release channel.
  • the mesh foil protection method adopts a co-curing molding method.
  • a conductive grid of aluminum or copper is attached to the surface of the structure or buried under the outermost layer of the structure.
  • the resistivity of copper is 1.75 ⁇ 10 -8 ⁇ m.
  • the electrical conductivity is better than that of aluminum, and the large-density copper grid is conducive to the flow of instantaneous currents.
  • Aluminum and copper grids can be laminated, sprayed and electroplated. When the grids are cured on the composite structure, they can withstand a current of 200kA (generally a lightning current of 100kA) without damage. When repairing, the maintenance personnel only need to peel off the damaged part, sand off the surface, and re-adhesive.
  • the surface layer protection method is suitable for situations where the requirements for electrical conductivity are not very high.
  • the more commonly used is to spray antistatic coatings on the surface of composite materials.
  • Antistatic coatings are composed of resin or rubber, conductive fillers and solvents that play a role in bonding.
  • the conductive fillers can be some kind of metal particles. These metal particles are polymerized.
  • the material forms a continuous conductive network chain, thereby discharging charges.
  • the commonly used surface layer protection method is the decorative strip method, which is to inlay decorative conductive metal strips on the lacquer layer. Now some people have developed the decorative strip into a decorative layer, which can be pasted like wallpaper, which not only replaces spray paint but also has a conductive effect, and can be easily pasted or torn off.
  • Aircraft composite materials mainly protect the aircraft by adding a conductive functional layer on the surface to discharge static charges or current on the surface in a timely manner, and prevent lightning and lightning from damaging the aircraft.
  • the measures to increase the conductive functional layer mainly include flame spraying aluminum coating on the surface of the composite material, bonding metal mesh, and bonding aluminum foil.
  • Existing conductive functional layers are all metallic materials. Because of their high density, they will undoubtedly increase the weight of the aircraft.
  • the difference in material properties between metals and composite materials causes interface coordination and potential corrosion problems, requiring additional insulation layers.
  • the present invention proposes a carbon nanotube film/composite material forming method and a manufactured lightning protection structure.
  • the lightning protection structure solves the problems of large weight of the existing composite lightning protection conductive functional layer and poor fusion of the body composite material and complicated procedures, and the lightning protection structure can be integrally formed in one step.
  • a carbon nanotube film/composite material lightning protection structure comprising:
  • Carbon nanotube film used as a conductive layer Carbon nanotube film used as a conductive layer
  • Composite materials including fibers and resin filled in fibers
  • the carbon nanotube film, the glue film and the composite material are arranged in sequence.
  • the fiber is a dry fiber, and the material is not limited, and it may be carbon fiber or glass fiber.
  • the carbon nanotube film is a continuous high-conductivity ultra-light carbon nanotube film.
  • the thickness of the carbon nanotube film is not less than 15 ⁇ m, and the thickness is adjustable.
  • the areal density of the carbon nanotube film is not greater than 10 g/m 2 .
  • the carbon nanotube film is prepared by a floating catalytic chemical weather deposition method.
  • the electrical conductivity of the carbon nanotube film is 10 4 -10 6 s/m, and the electrical conductivity of the carbon nanotube film in various directions can be adjusted, which can be adjusted by adjusting the orientation of the carbon nanotubes in the carbon nanotube film. Conductivity in all directions.
  • the density of the composite material is 1.5-1.8 g/cm 3 .
  • the carbon nanotube film used in the lightning protection structure is very light, it basically does not increase the weight of the composite material. Therefore, the density of the lightning protection structure is 1.5-1.8 g/cm 3 .
  • methods such as metal deposition, covalent bonding, heteroatom doping, and resin compounding are used to improve the transfer of electrons between the carbon nanotube interfaces in the carbon nanotube film to further increase the conductivity of the carbon nanotube film .
  • Another object of the present invention is to provide a method for forming the above-mentioned carbon nanotube film/composite lightning protection structure, which is based on a high-conductivity ultra-light carbon nanotube film to construct a multi-scale nanocomposite lightning protection layer Design;
  • the molding method adopts a low-cost liquid molding one-step method to obtain an ultra-light carbon nanotube film/composite lightning protection structure as a whole; solves the problem of the heavy weight of the existing composite lightning protection conductive functional layer and the poor integration of the body composite material and the process
  • a multi-scale ultra-light carbon nanotube composite lightning protection structure can be integrally formed in one step.
  • the multi-scale means that the lightning protection structure has a structure of nanometer/micrometer/mm/meter scale: a single carbon nanotube is nanometer scale, a carbon nanotube film is micrometer scale, and the thickness of the composite material is millimeter scale. , The composite material is meter-level.
  • the molding method includes the following steps:
  • the mold release agent is AXEL CX-500, PMR-EZ or other types of mold release agents, which are applied after cleaning and assembly, and assisted in demolding after curing.
  • the laying in the S2 adopts manual laying or automatic laying
  • the automatic laying adopts an automatic tape laying machine or an automatic silk laying machine.
  • the curing in S3 adopts a curing oven for curing.
  • the carbon nanotube film/composite material lightning protection structure is prepared by using an autoclave; specifically: the carbon nanotube film, the glue film and the prepreg are laid down in sequence , Being placed in a hot autoclave and solidified to obtain the carbon nanotube film/composite lightning protection structure.
  • the vacuum degree after vacuuming in S3 is above -90KPa.
  • the curing temperature and curing time in S3 vary with different resin systems.
  • the curing temperature of the commonly used aviation resin system is 180°C, and the curing time is 2h.
  • the amount of the liquid resin poured in is calculated backwards from the fiber content of the final composite material; the resin enters through the glue inlet, and the excess resin overflows from the glue outlet.
  • the volume content of the fiber is about 55%, and the sum of the volume of the resin and the fiber is 100%.
  • the peelable cloth and the isolation film are auxiliary materials to protect the surface of the auxiliary materials, and the diversion net is the resin diversion medium in the liquid molding process to aid the resin infiltration of the dry fiber preform;
  • an inner vacuum bag It is used to provide the required vacuum environment to suck in the resin; the ventilation plays a role of air conduction, and the pressure in each area in the vacuum bag is uniform; on the one hand, the outer vacuum bag prevents air leakage when the inner vacuum bag is damaged, and is used to ensure the vacuum; On the other hand, the external uniform pressure is provided without leakage of the inner vacuum bag, so that the pressure in the thickness direction of each area of the composite material is the same, and the thickness is uniform.
  • the forming method of the present invention uses continuous high-conductivity ultra-light carbon nanotube film as the conductive functional layer, with low density and an areal density not greater than 10g/m 2 , and it is the same carbon material as the composite material, and has good fusion with the composite material. Reduce interface problems.
  • methods such as metal deposition, covalent bonding, heteroatom doping, and resin compounding can be used to improve the conductivity of the carbon nanotube film.
  • the molding method of the present invention is compared with the existing secondary process used for the composite of the metal conductive functional layer and the bulk composite material.
  • the molding method of the present invention adopts a liquid molding one-step method to prepare a carbon nanotube film/composite lightning protection structure , No need for secondary bonding, which simplifies the process.
  • a layer of glue film is used between the high-conductivity ultra-light carbon nanotube film and the composite material, and no additional insulating glass fiber layer is required; it can maintain the conductivity of the carbon nanotube film and ensure lightning
  • the protective effect can also reduce the weight and improve the interface bonding effect between the conductive functional layer and the composite material.
  • the lightning protection structure of the present invention uses carbon nanotube film to replace the existing copper mesh, aluminum foil and other metal conductive functional layers.
  • the continuous high-conductivity ultra-light carbon nano As a conductive functional layer, the tube film has a low density, and is the same carbon material as the main composite material, and has good interface fusion.
  • the lightning protection structure of the present invention is to avoid the glass fiber insulating layer with increased potential corrosion, the multi-scale ultra-light carbon nanotube film proposed by this method is composited with the body A layer of glue film is used between the materials instead of an additional insulating glass fiber layer, which can not only maintain the conductivity of the carbon nanotube film to ensure the lightning protection effect, but also reduce the weight and improve the interface bonding between the conductive functional layer and the main composite material effect.
  • Fig. 1 is a schematic structural diagram of a lightning protection structure in an embodiment of the present invention.
  • Fig. 2 is a microscopic morphology diagram of a carbon nanotube film in an embodiment of the present invention.
  • Fig. 3 is a schematic diagram of the structure of laying down various layers in the forming method of the embodiment of the present invention.
  • FIG. 4 is a schematic diagram of the positions where the liquid resin is introduced and discharged in the molding method of the embodiment of the present invention.
  • Fig. 5 is a schematic flow chart of a forming method according to an embodiment of the present invention.
  • 1 is a carbon nanotube film
  • 2 is an adhesive film
  • 3 is a composite material
  • 31 is a fiber.
  • This embodiment proposes a carbon nanotube film/composite material lightning protection structure, as shown in FIG. 1 and FIG. 2, the lightning protection structure includes:
  • Carbon nanotube film used as a conductive layer Carbon nanotube film used as a conductive layer
  • Composite materials including fibers and resin filled in fibers
  • the carbon nanotube film, the glue film and the composite material are arranged in sequence.
  • the fiber is dry fiber, and the material is not limited, and it can be carbon fiber or glass fiber.
  • the carbon nanotube film is a continuous high-conductivity ultra-light carbon nanotube film.
  • the thickness of the carbon nanotube film is not less than 15 ⁇ m, and the thickness is adjustable.
  • the areal density of the carbon nanotube film is not greater than 10 g/m 2 .
  • the carbon nanotube film is prepared by a floating catalytic chemical meteorological deposition method.
  • the electrical conductivity of the carbon nanotube film is 10 4 -10 6 s/m, which is adjustable.
  • the density of the composite material is 1.5-1.8 g/cm 3 .
  • the carbon nanotube film used in the lightning protection structure is very light, it basically does not increase the weight of the composite material. Therefore, the density of the lightning protection structure is 1.5-1.8 g/cm 3 .
  • Methods such as metal deposition, covalent bonding, heteroatom doping, and resin compounding are used to improve the transfer of electrons between the carbon nanotube interfaces in the carbon nanotube film to further increase the electrical conductivity of the carbon nanotube film.
  • This embodiment provides a molding method for preparing the carbon nanotube film/composite lightning protection structure in Example 1.
  • the molding method is based on a highly conductive ultra-light carbon nanotube film for multi-scale nanocomposite lightning protection
  • the structure design of the layer; the forming method adopts low-cost liquid forming one-step method to obtain an ultra-light carbon nanotube film/composite lightning protection structure as a whole; solves the problem that the existing composite lightning protection conductive functional layer is heavy and the main composite material is integrated Due to poor performance and complex procedures, a multi-scale ultra-light carbon nanotube composite lightning protection structure can be integrally formed in one step.
  • the multi-scale means that the lightning protection structure has a structure of nanometer/micrometer/mm/meter level: single carbon nanotube is nanometer level, carbon nanotube film is micrometer level, composite material thickness is millimeter level, composite material It is a meter level.
  • the molding method includes the following steps:
  • the mold release agent is AXEL CX-500, PMR-EZ or other equivalent functional brands, and is applied after cleaning the mold, and assists the mold release after curing.
  • the laying in the S2 adopts manual laying or automatic laying
  • the automatic laying adopts an automatic tape laying machine or an automatic silk laying machine.
  • the curing described in S3 adopts an autoclave or a curing oven for curing.
  • the vacuum degree of vacuum in S3 is above -90KPAa.
  • the curing temperature and curing time in S3 vary with different resin systems.
  • the curing temperature of the commonly used aviation resin system is 180°C and the curing time is 2h.
  • the amount of the liquid resin poured in is calculated backwards from the fiber content of the final composite material; the resin enters through the glue inlet, and the excess resin overflows from the glue outlet.
  • the volume content of the fiber is about 55%, and the sum of the volume of the resin and the fiber is 100%.
  • the peelable cloth and the isolation film are auxiliary materials to protect the surface of the auxiliary materials
  • the diversion net is the resin diversion medium in the liquid molding process
  • the auxiliary resin infiltrates the dry fiber preform
  • the inner vacuum bag is used to provide The vacuum environment is required to inhale the resin
  • the ventilation plays a role of air conduction, and the pressure of each area in the vacuum bag is even
  • the outer vacuum bag prevents air leakage when the inner vacuum bag is damaged, and is used to ensure the vacuum
  • the internal vacuum bag provides uniform external pressure without leaking, so that the pressure in the thickness direction of each area of the composite material is the same, and the thickness is uniform.
  • This embodiment provides a method for preparing the carbon nanotube film/composite lightning protection structure in Example 1.
  • the composite material is a prepreg
  • the carbon nanotube film/composite is prepared by using a hot autoclave.
  • Material lightning protection structure specifically: the carbon nanotube film, the glue film and the prepreg are laid in sequence, and then placed in a hot autoclave for curing to obtain the carbon nanotube film/composite material lightning protection structure.

Abstract

A carbon nanotube thin film/composite material forming method and a manufactured lightning protection structure. In the forming method, a low-cost liquid forming one-step method is adopted to integrally obtain an ultralight carbon nanotube thin film/composite material lightning protection structure. The lightning protection structure comprises: a carbon nanotube thin film used as a conductive layer, a composite material comprising fibers and a resin with which the fibers are filled, and an adhesive film used for electric insulation between the composite material and the carbon nanotube thin film, wherein the carbon nanotube thin film, the adhesive film, and the composite material are sequentially provided. The lightning protection structure can be integrally formed by means of the one-step method.

Description

碳纳米管薄膜/复合材料成型方法及制成的闪电防护结构Carbon nanotube film/composite material forming method and lightning protection structure made 技术领域Technical field
本发明属于飞机复合材料闪电防护技术领域，具体涉及一种碳纳米管薄膜/复合材料成型方法及制成的闪电防护结构。The invention belongs to the technical field of aircraft composite material lightning protection, and in particular relates to a carbon nanotube film/composite material forming method and a manufactured lightning protection structure.
背景技术Background technique
飞机在服役过程中，不可避免的要遭遇雷电天气。相比金属材料，复合材料导电性差，当雷电闪击复合材料构件时，如果没有采取合适的闪电防护措施，构件很难在短时间内将积聚的电流导走，从而导致温度上升，使复合材料产生深度分层或被严重烧蚀，危及正常使用，因此必须对复合材料构件进行闪电防护。目前，对复合材料进行闪电防护措施主要通过在其表面增加导电功能层，包括表面火焰喷涂铝涂层、粘接金属网及粘接铝箔等。When the aircraft is in service, it will inevitably encounter thunder and lightning weather. Compared with metal materials, composite materials have poor electrical conductivity. When lightning strikes composite material components, if appropriate lightning protection measures are not taken, it is difficult for the components to conduct the accumulated current in a short time, which will cause the temperature to rise and cause the composite material to produce Deep stratification or severe ablation, endangering normal use, so composite components must be protected against lightning. At present, the lightning protection measures for composite materials are mainly by adding conductive functional layers on the surface, including surface flame spraying aluminum coating, bonding metal mesh, and bonding aluminum foil.
铝涂层防护法，是在复合材料基体上采用转移法进行火焰喷涂来制备铝涂层防护层，即转移膜法，也可以采用等离子电镀法来制备铝涂层，涂层最佳厚度为0.20mm。铝的电阻率为2.83×10 -8Ω·m，其导电性能良好，复合材料表面喷涂铝涂层后会形成一层连续的导电层，该导电层为飞机因摩擦或感应而产生的静电荷和雷击产生的强电流提供了一个释放通道。 The aluminum coating protection method is to prepare the aluminum coating protection layer by flame spraying on the composite material matrix, that is, the transfer film method, or the plasma electroplating method to prepare the aluminum coating. The optimal thickness of the coating is 0.20 mm. The resistivity of aluminum is 2.83×10 -8 Ω·m, and its electrical conductivity is good. After the aluminum coating is sprayed on the surface of the composite material, a continuous conductive layer will be formed. This conductive layer is the electrostatic charge generated by the aircraft due to friction or induction And the strong current generated by lightning provides a release channel.
网箔保护法采用的是共固化成型的方式，将铝或铜导电格网贴在结构表面或埋在结构最外层下面，其中铜的电阻率为1.75×10 -8Ω·m，它的导电性能要优于铝，大密度的铜网格有利于瞬间大流的疏导。铝和铜格网可以层压、喷涂和电镀，当格网固化到复合材料结构上后，其可承受200kA的电流(一般雷击电流为100kA)而无损伤。维修人员在修理时只要将其损坏部份剥掉，砂除表面，重新胶粘即可。 The mesh foil protection method adopts a co-curing molding method. A conductive grid of aluminum or copper is attached to the surface of the structure or buried under the outermost layer of the structure. The resistivity of copper is 1.75×10 -8 Ω·m. The electrical conductivity is better than that of aluminum, and the large-density copper grid is conducive to the flow of instantaneous currents. Aluminum and copper grids can be laminated, sprayed and electroplated. When the grids are cured on the composite structure, they can withstand a current of 200kA (generally a lightning current of 100kA) without damage. When repairing, the maintenance personnel only need to peel off the damaged part, sand off the surface, and re-adhesive.
表面层保护法，适用于在对导电性能要求不是很高的情况。较为常用的是在复合材料表面喷涂防静电涂料，防静电涂料是由起粘结作用的树脂或橡胶以及导电填充剂和溶剂等组成，导电填充剂可以是某种金属粒子，这些金属粒子在聚合物中形成连续的导电网链，从而排放电荷。此外，常用的表面层保护法还有装饰条法，也就是在漆层面上镶上装饰的导电金属条。现在有人已将装饰条发展为装饰层，能像墙纸一样贴上去，既代替了喷漆又兼有导电作用，并能容易地贴上或撕下。The surface layer protection method is suitable for situations where the requirements for electrical conductivity are not very high. The more commonly used is to spray antistatic coatings on the surface of composite materials. Antistatic coatings are composed of resin or rubber, conductive fillers and solvents that play a role in bonding. The conductive fillers can be some kind of metal particles. These metal particles are polymerized. The material forms a continuous conductive network chain, thereby discharging charges. In addition, the commonly used surface layer protection method is the decorative strip method, which is to inlay decorative conductive metal strips on the lacquer layer. Now some people have developed the decorative strip into a decorative layer, which can be pasted like wallpaper, which not only replaces spray paint but also has a conductive effect, and can be easily pasted or torn off.
飞机复合材料主要通过在其表面增加导电功能层，将其表面静电荷或电流及 时排放的方式来保护飞机，防止雷击和闪电破坏机体。目前，增加导电功能层的措施主要有在复合材料表面火焰喷涂铝涂层、粘接金属网及粘接铝箔等。现有的导电功能层都是金属材料，因其密度较大，无疑会增加飞机的重量；此外，金属与复合材料之间的材料性能差异，造成界面配合和电位腐蚀问题，需要额外引入绝缘层，也导致重量增加；此外，增加导电功能层的措施需要二次工艺，工艺复杂，造成较高的成本。Aircraft composite materials mainly protect the aircraft by adding a conductive functional layer on the surface to discharge static charges or current on the surface in a timely manner, and prevent lightning and lightning from damaging the aircraft. At present, the measures to increase the conductive functional layer mainly include flame spraying aluminum coating on the surface of the composite material, bonding metal mesh, and bonding aluminum foil. Existing conductive functional layers are all metallic materials. Because of their high density, they will undoubtedly increase the weight of the aircraft. In addition, the difference in material properties between metals and composite materials causes interface coordination and potential corrosion problems, requiring additional insulation layers. , It also leads to an increase in weight; in addition, measures to increase the conductive functional layer require a secondary process, which is complicated and causes higher costs.
此外，也有研究采用不同的分散技术将粉体碳纳米管分散到复合材料树脂基体中制备导电复合材料，虽然解决了不同材料间的性能差异问题，但是由于粉体碳纳米管纳米级尺寸团聚问题导致的分散困难，复合材料中导电碳纳米管含量低于2％，制备的复合材料导电性能较差，且碳纳米管的加入导致树脂粘度增大，影响复合材料工艺性。In addition, there are also studies using different dispersion techniques to disperse powdered carbon nanotubes into the composite resin matrix to prepare conductive composite materials. Although the performance difference between different materials has been solved, the problem of agglomeration of powdered carbon nanotubes at the nanometer scale has been solved. The resulting dispersion difficulties, the content of conductive carbon nanotubes in the composite material is less than 2%, the prepared composite material has poor electrical conductivity, and the addition of carbon nanotubes causes the resin viscosity to increase, which affects the manufacturability of the composite material.
综上，针对以上缺点，需要提供一种技术方案来克服或至少减轻现有技术的至少一个上述缺陷。In summary, in view of the above shortcomings, it is necessary to provide a technical solution to overcome or at least alleviate at least one of the above shortcomings of the prior art.
发明内容Summary of the invention
为解决上述问题，本发明提出一种碳纳米管薄膜/复合材料成型方法及制成的闪电防护结构。所述闪电防护结构解决了现有复合材料闪电防护导电功能层重量较大与本体复合材料融合性差和工序复杂问题，可一步法整体成型所述闪电防护结构。In order to solve the above-mentioned problems, the present invention proposes a carbon nanotube film/composite material forming method and a manufactured lightning protection structure. The lightning protection structure solves the problems of large weight of the existing composite lightning protection conductive functional layer and poor fusion of the body composite material and complicated procedures, and the lightning protection structure can be integrally formed in one step.
本发明是通过以下技术方案实现的：The present invention is realized through the following technical solutions:
一种碳纳米管薄膜/复合材料闪电防护结构，所述闪电防护结构包括：A carbon nanotube film/composite material lightning protection structure, the lightning protection structure comprising:
用作导电层的碳纳米管薄膜；Carbon nanotube film used as a conductive layer;
复合材料，包括纤维和填充在纤维中的树脂；Composite materials, including fibers and resin filled in fibers;
胶膜，用于对所述复合材料和碳纳米管薄膜之间的电绝缘；An adhesive film for electrical insulation between the composite material and the carbon nanotube film;
所述碳纳米管薄膜、胶膜和复合材料依次设置。The carbon nanotube film, the glue film and the composite material are arranged in sequence.
进一步地，所述纤维为干纤维，材料不限，可以是碳纤维或玻纤。Further, the fiber is a dry fiber, and the material is not limited, and it may be carbon fiber or glass fiber.
进一步地，所述碳纳米管薄膜为连续高导电超轻碳纳米管薄膜。Further, the carbon nanotube film is a continuous high-conductivity ultra-light carbon nanotube film.
进一步地，所述碳纳米管薄膜的厚度不小于15μm，厚度可调。Further, the thickness of the carbon nanotube film is not less than 15 μm, and the thickness is adjustable.
进一步地，所述碳纳米管薄膜的面密度不大于10g/m 2。 Further, the areal density of the carbon nanotube film is not greater than 10 g/m 2 .
进一步地，所述碳纳米管薄膜采用浮动催化化学气象沉积法制备得到。Further, the carbon nanotube film is prepared by a floating catalytic chemical weather deposition method.
进一步地，所述碳纳米管薄膜的电导率为10 4-10 6s/m，且碳纳米管薄膜的各个方向的电导率可调，可以通过调整碳纳米管薄膜内的碳纳米管取向调整各个方向的电导率。 Further, the electrical conductivity of the carbon nanotube film is 10 4 -10 6 s/m, and the electrical conductivity of the carbon nanotube film in various directions can be adjusted, which can be adjusted by adjusting the orientation of the carbon nanotubes in the carbon nanotube film. Conductivity in all directions.
进一步地，所述复合材料的密度为1.5～1.8g/cm 3。 Further, the density of the composite material is 1.5-1.8 g/cm 3 .
进一步地，所述闪电防护结构因采用的碳纳米管薄膜质量很轻，基本上不会增加复合材料的重量，因此，所述闪电防护结构的密度为1.5～1.8g/cm 3。 Further, because the carbon nanotube film used in the lightning protection structure is very light, it basically does not increase the weight of the composite material. Therefore, the density of the lightning protection structure is 1.5-1.8 g/cm 3 .
进一步地，采用金属沉积、共价键连结、杂原子掺杂、树脂复合等方法以提高所述碳纳米管薄膜中碳纳米管界面间电子的传递来进一步提高所述碳纳米管薄膜的电导率。Further, methods such as metal deposition, covalent bonding, heteroatom doping, and resin compounding are used to improve the transfer of electrons between the carbon nanotube interfaces in the carbon nanotube film to further increase the conductivity of the carbon nanotube film .
本发明的另一目的在于提供上述碳纳米管薄膜/复合材料闪电防护结构的成型方法，所述成型方法以高导电超轻碳纳米管薄膜为基础，进行多尺度纳米复合材料闪电防护层的结构设计；所述成型方法采用低成本液体成型一步法整体得到超轻碳纳米管薄膜/复合材料闪电防护结构；解决了现有复合材料闪电防护导电功能层重量较大与本体复合材料融合性差和工序复杂问题，可一步法整体成型多尺度超轻碳纳米管复合材料闪电防护结构。Another object of the present invention is to provide a method for forming the above-mentioned carbon nanotube film/composite lightning protection structure, which is based on a high-conductivity ultra-light carbon nanotube film to construct a multi-scale nanocomposite lightning protection layer Design; The molding method adopts a low-cost liquid molding one-step method to obtain an ultra-light carbon nanotube film/composite lightning protection structure as a whole; solves the problem of the heavy weight of the existing composite lightning protection conductive functional layer and the poor integration of the body composite material and the process For complex problems, a multi-scale ultra-light carbon nanotube composite lightning protection structure can be integrally formed in one step.
进一步地，所述多尺度是指所述闪电防护结构是具有纳米/微米/毫米/米级的结构：单根碳纳米管是纳米级，碳纳米管薄膜是微米级，复合材料厚度是毫米级，复合材料是米级。Further, the multi-scale means that the lightning protection structure has a structure of nanometer/micrometer/mm/meter scale: a single carbon nanotube is nanometer scale, a carbon nanotube film is micrometer scale, and the thickness of the composite material is millimeter scale. , The composite material is meter-level.
进一步地，所述成型方法包括以下步骤：Further, the molding method includes the following steps:
S1，选取液体成型工艺用工装，清理工装并涂脱模剂；S1, select tooling for liquid molding process, clean the tooling and apply release agent;
S2，工装从下到上依次铺放第一可剥布、碳纳米管薄膜、胶膜、纤维、第二可剥布、隔离膜、导流网、内真空袋、透气毡和外真空袋；所述内真空袋和外真空外与所述工装接触处密封，采用密封胶密封；S2: Lay the first peelable cloth, the carbon nanotube film, the glue film, the fiber, the second peelable cloth, the isolation film, the deflector net, the inner vacuum bag, the air felt, and the outer vacuum bag in sequence from bottom to top on the tooling; The contact between the inner vacuum bag and the outer vacuum bag and the tooling is sealed, and sealed with a sealant;
S3，在抽真空作用下，将液体树脂从所述内真空袋和外真空袋的进胶口导入、出胶口导出，直至所述液体树脂完全浸润S2中的纤维，再固化所述液体树脂；S3: Under the action of vacuuming, the liquid resin is introduced from the glue inlet and the glue outlet of the inner vacuum bag and the outer vacuum bag until the liquid resin completely infiltrates the fibers in S2, and then the liquid resin is cured ；
S4，所述液体树脂固化成型后，拆除第一可剥布、第二可剥布、隔离膜、导流网、内真空袋、透气毡和外真空袋，得到所述碳纳米管薄膜/复合材料闪电防护结构。S4: After the liquid resin is cured and formed, the first peelable cloth, the second peelable cloth, the isolation film, the guide net, the inner vacuum bag, the air felt, and the outer vacuum bag are removed to obtain the carbon nanotube film/composite Material lightning protection structure.
进一步地，所述脱模剂为AXEL CX-500、PMR-EZ或其它型号的脱模剂，在清 理工装后涂覆，固化后辅助脱模。Further, the mold release agent is AXEL CX-500, PMR-EZ or other types of mold release agents, which are applied after cleaning and assembly, and assisted in demolding after curing.
进一步地，所述S2中的铺放采用手工铺放或自动铺放，自动铺放采用自动铺带机或自动铺丝机。Further, the laying in the S2 adopts manual laying or automatic laying, and the automatic laying adopts an automatic tape laying machine or an automatic silk laying machine.
进一步地，S3中所述固化采用固化炉进行固化。Further, the curing in S3 adopts a curing oven for curing.
进一步地，所述复合材料为预浸料时，采用热压罐制备得到所述碳纳米管薄膜/复合材料闪电防护结构；具体为：将碳纳米管薄膜、胶膜和预浸料依次铺放，置于热压罐中固化得到所述碳纳米管薄膜/复合材料闪电防护结构。Further, when the composite material is a prepreg, the carbon nanotube film/composite material lightning protection structure is prepared by using an autoclave; specifically: the carbon nanotube film, the glue film and the prepreg are laid down in sequence , Being placed in a hot autoclave and solidified to obtain the carbon nanotube film/composite lightning protection structure.
进一步地，S3中抽真空后的真空度为-90KPa以上。Further, the vacuum degree after vacuuming in S3 is above -90KPa.
进一步地，S3中固化的温度及固化时间随着不同树脂体系不同而有异，常用的航空树脂体系固化温度为180℃，固化时间为2h。Furthermore, the curing temperature and curing time in S3 vary with different resin systems. The curing temperature of the commonly used aviation resin system is 180°C, and the curing time is 2h.
进一步地，所述液体树脂灌入的量由最终复合材料的纤维含量倒推计算；树脂由进胶口进入，多余树脂由出胶口溢出。Further, the amount of the liquid resin poured in is calculated backwards from the fiber content of the final composite material; the resin enters through the glue inlet, and the excess resin overflows from the glue outlet.
进一步地，所述复合材料中，纤维的体积含量为55％左右，树脂和纤维的体积之和是100％。Further, in the composite material, the volume content of the fiber is about 55%, and the sum of the volume of the resin and the fiber is 100%.
进一步地，所述成型方法中，可剥布、隔离膜为辅助材料，保护辅助材料表面，导流网为液体成型工艺中的树脂导流介质，辅助树脂浸润干纤维预成型体；内真空袋用于提供所需真空环境，以吸入树脂；透气起到导气作用，时真空袋内各区域压力均匀；外真空袋一方面在内真空袋破损的情况下防止漏气，用于保证真空；另一方面内真空袋不漏的情况下提供外在均匀压力，使复合材料各区域厚度方向压力相同，厚度均匀。Further, in the molding method, the peelable cloth and the isolation film are auxiliary materials to protect the surface of the auxiliary materials, and the diversion net is the resin diversion medium in the liquid molding process to aid the resin infiltration of the dry fiber preform; an inner vacuum bag It is used to provide the required vacuum environment to suck in the resin; the ventilation plays a role of air conduction, and the pressure in each area in the vacuum bag is uniform; on the one hand, the outer vacuum bag prevents air leakage when the inner vacuum bag is damaged, and is used to ensure the vacuum; On the other hand, the external uniform pressure is provided without leakage of the inner vacuum bag, so that the pressure in the thickness direction of each area of the composite material is the same, and the thickness is uniform.
本发明具有如下有益技术效果：The present invention has the following beneficial technical effects:
1)本发明的成型方法采用连续高导电超轻碳纳米管薄膜作为导电功能层，密度低，面密度不大于10g/m 2，且与复合材料同为碳材料，与复合材料融合性好，降低界面问题。此外，可利用金属沉积、共价键连结、杂原子掺杂、树脂复合等方法提高碳纳米管薄膜的导电性。 1) The forming method of the present invention uses continuous high-conductivity ultra-light carbon nanotube film as the conductive functional layer, with low density and an areal density not greater than 10g/m 2 , and it is the same carbon material as the composite material, and has good fusion with the composite material. Reduce interface problems. In addition, methods such as metal deposition, covalent bonding, heteroatom doping, and resin compounding can be used to improve the conductivity of the carbon nanotube film.
2)本发明的成型方法相比于现有的金属导电功能层与本体复合材料复合采用的二次工艺，本发明的成型方法采用液体成型一步法制备得到碳纳米管薄膜/复合材料闪电防护结构，不需要二次胶接，简化了工艺。2) The molding method of the present invention is compared with the existing secondary process used for the composite of the metal conductive functional layer and the bulk composite material. The molding method of the present invention adopts a liquid molding one-step method to prepare a carbon nanotube film/composite lightning protection structure , No need for secondary bonding, which simplifies the process.
3)本发明的闪电防护结构中，高导电超轻碳纳米管薄膜与复合材料间采用 一层胶膜，不必额外采用绝缘玻纤层；既可保持碳纳米管薄膜的导电率，保证了闪电防护效果，又可减轻重量，改善导电功能层与复合材料间的界面粘结效果。3) In the lightning protection structure of the present invention, a layer of glue film is used between the high-conductivity ultra-light carbon nanotube film and the composite material, and no additional insulating glass fiber layer is required; it can maintain the conductivity of the carbon nanotube film and ensure lightning The protective effect can also reduce the weight and improve the interface bonding effect between the conductive functional layer and the composite material.
4)本发明的闪电防护结构采用碳纳米管薄膜代替现有的铜网、铝箔等金属导电功能层，相比于现有的铜网、铝箔等金属导电功能层，连续高导电超轻碳纳米管薄膜作为导电功能层，密度低，且与本体复合材料同为碳材料，界面融合性好。4) The lightning protection structure of the present invention uses carbon nanotube film to replace the existing copper mesh, aluminum foil and other metal conductive functional layers. Compared with the existing copper mesh, aluminum foil and other metal conductive functional layers, the continuous high-conductivity ultra-light carbon nano As a conductive functional layer, the tube film has a low density, and is the same carbon material as the main composite material, and has good interface fusion.
5)本发明的闪电防护结构相比于现有的金属导电功能层与本体复合材料间，为避免电位腐蚀增加的玻纤绝缘层，本方法提出的多尺度超轻碳纳米管薄膜与本体复合材料间采用一层胶膜，不必额外采用绝缘玻纤层，既可保持碳纳米管薄膜的导电率从而保证闪电防护效果，又可减轻重量，改善导电功能层与本体复合材料间的界面粘结效果。5) Compared with the existing metal conductive functional layer and the body composite material, the lightning protection structure of the present invention is to avoid the glass fiber insulating layer with increased potential corrosion, the multi-scale ultra-light carbon nanotube film proposed by this method is composited with the body A layer of glue film is used between the materials instead of an additional insulating glass fiber layer, which can not only maintain the conductivity of the carbon nanotube film to ensure the lightning protection effect, but also reduce the weight and improve the interface bonding between the conductive functional layer and the main composite material effect.
附图说明Description of the drawings
图1为本发明实施例中闪电防护结构的结构示意图。Fig. 1 is a schematic structural diagram of a lightning protection structure in an embodiment of the present invention.
图2本发明实施例中碳纳米管薄膜微观形貌图。Fig. 2 is a microscopic morphology diagram of a carbon nanotube film in an embodiment of the present invention.
图3为本发明实施例的成型方法中铺放各层的结构示意图。Fig. 3 is a schematic diagram of the structure of laying down various layers in the forming method of the embodiment of the present invention.
图4为本发明实施例的成型方法中液体树脂导入及导出的位置示意图。FIG. 4 is a schematic diagram of the positions where the liquid resin is introduced and discharged in the molding method of the embodiment of the present invention.
图5为本发明实施例的成型方法的流程示意图。Fig. 5 is a schematic flow chart of a forming method according to an embodiment of the present invention.
附图标记说明：1为碳纳米管薄膜，2为胶膜，3为复合材料，31为纤维。Description of reference signs: 1 is a carbon nanotube film, 2 is an adhesive film, 3 is a composite material, and 31 is a fiber.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例及说明书附图，对本发明进行进一步详细描述。应当理解，此处所描述的具体实施例仅仅用于解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes the present invention in detail with reference to the embodiments and the accompanying drawings of the specification. It should be understood that the specific embodiments described here are only used to explain the present invention, but not used to limit the present invention.
相反，本发明涵盖任何由权利要求定义的在本发明的精髓和范围上做的替代、修改、等效教学方法以及方案。进一步，为了使公众对本发明有更好的了解，在下文对本发明的细节描述中，详尽描述了一些特定的细节部分。对本领域技术人员来说没有这些细节部分的描述也可以完全理解本发明。On the contrary, the present invention covers any substitutions, modifications, equivalent teaching methods and solutions defined by the claims in the spirit and scope of the present invention. Further, in order to enable the public to have a better understanding of the present invention, in the following detailed description of the present invention, some specific details are described in detail. Those skilled in the art can fully understand the present invention without the description of these details.
应当明确，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。It should be clear that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
在本发明实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本发明。在本发明实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The singular forms of "a", "said" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.
实施例1Example 1
本实施例提出一种碳纳米管薄膜/复合材料闪电防护结构，如图1和图2所示，所述闪电防护结构包括：This embodiment proposes a carbon nanotube film/composite material lightning protection structure, as shown in FIG. 1 and FIG. 2, the lightning protection structure includes:
用作导电层的碳纳米管薄膜；Carbon nanotube film used as a conductive layer;
复合材料，包括纤维和填充在纤维中的树脂；Composite materials, including fibers and resin filled in fibers;
胶膜，用于对所述复合材料和碳纳米管薄膜之间的电绝缘；An adhesive film for electrical insulation between the composite material and the carbon nanotube film;
所述碳纳米管薄膜、胶膜和复合材料依次设置。The carbon nanotube film, the glue film and the composite material are arranged in sequence.
所述纤维为干纤维，材料不限，可以是碳纤维或玻纤。The fiber is dry fiber, and the material is not limited, and it can be carbon fiber or glass fiber.
所述碳纳米管薄膜为连续高导电超轻碳纳米管薄膜。The carbon nanotube film is a continuous high-conductivity ultra-light carbon nanotube film.
所述碳纳米管薄膜的厚度不小于15μm，厚度可调。The thickness of the carbon nanotube film is not less than 15 μm, and the thickness is adjustable.
所述碳纳米管薄膜的面密度不大于10g/m 2。 The areal density of the carbon nanotube film is not greater than 10 g/m 2 .
所述碳纳米管薄膜采用浮动催化化学气象沉积法制备得到。The carbon nanotube film is prepared by a floating catalytic chemical meteorological deposition method.
所述碳纳米管薄膜的电导率为10 4-10 6s/m，可调。 The electrical conductivity of the carbon nanotube film is 10 4 -10 6 s/m, which is adjustable.
所述复合材料的密度为1.5～1.8g/cm 3。 The density of the composite material is 1.5-1.8 g/cm 3 .
所述闪电防护结构因采用的碳纳米管薄膜质量很轻，基本上不会增加复合材料的重量，因此，所述闪电防护结构的密度为1.5～1.8g/cm 3。 Because the carbon nanotube film used in the lightning protection structure is very light, it basically does not increase the weight of the composite material. Therefore, the density of the lightning protection structure is 1.5-1.8 g/cm 3 .
采用金属沉积、共价键连结、杂原子掺杂、树脂复合等方法以提高所述碳纳米管薄膜中碳纳米管界面间电子的传递来进一步提高所述碳纳米管薄膜的电导率。Methods such as metal deposition, covalent bonding, heteroatom doping, and resin compounding are used to improve the transfer of electrons between the carbon nanotube interfaces in the carbon nanotube film to further increase the electrical conductivity of the carbon nanotube film.
实施例2Example 2
本实施例提供一种制备实施例1中的碳纳米管薄膜/复合材料闪电防护结构的成型方法，所述成型方法以高导电超轻碳纳米管薄膜为基础，进行多尺度纳米复合材料闪电防护层的结构设计；所述成型方法采用低成本液体成型一步法整体得到超轻碳纳米管薄膜/复合材料闪电防护结构；解决了现有复合材料闪电防护导电功能层重量较大与本体复合材料融合性差和工序复杂问题，可一步法整体成 型多尺度超轻碳纳米管复合材料闪电防护结构。This embodiment provides a molding method for preparing the carbon nanotube film/composite lightning protection structure in Example 1. The molding method is based on a highly conductive ultra-light carbon nanotube film for multi-scale nanocomposite lightning protection The structure design of the layer; the forming method adopts low-cost liquid forming one-step method to obtain an ultra-light carbon nanotube film/composite lightning protection structure as a whole; solves the problem that the existing composite lightning protection conductive functional layer is heavy and the main composite material is integrated Due to poor performance and complex procedures, a multi-scale ultra-light carbon nanotube composite lightning protection structure can be integrally formed in one step.
所述多尺度是指所述闪电防护结构是具有纳米/微米/毫米/米级的结构：单根碳纳米管是纳米级，碳纳米管薄膜是微米级，复合材料厚度是毫米级，复合材料是米级。The multi-scale means that the lightning protection structure has a structure of nanometer/micrometer/mm/meter level: single carbon nanotube is nanometer level, carbon nanotube film is micrometer level, composite material thickness is millimeter level, composite material It is a meter level.
参考图3、图4和图5，所述成型方法包括以下步骤：Referring to Figure 3, Figure 4 and Figure 5, the molding method includes the following steps:
S1，选取液体成型工艺用工装，清理工装并涂脱模剂；S1, select tooling for liquid molding process, clean the tooling and apply release agent;
S2，工装从下到上依次铺放第一可剥布、碳纳米管薄膜、胶膜、纤维、第二可剥布、隔离膜、导流网、内真空袋、透气毡和外真空袋；所述内真空袋和外真空外与所述工装接触处密封，采用密封胶密封；S2: Lay the first peelable cloth, the carbon nanotube film, the glue film, the fiber, the second peelable cloth, the isolation film, the deflector net, the inner vacuum bag, the air felt, and the outer vacuum bag in sequence from bottom to top on the tooling; The contact between the inner vacuum bag and the outer vacuum bag and the tooling is sealed, and sealed with a sealant;
S3，在抽真空作用下，将液体树脂从所述内真空袋和外真空袋的进胶口导入、出胶口导出，直至所述液体树脂完全浸润S2中的纤维，再固化所述液体树脂；S3: Under the action of vacuuming, the liquid resin is introduced from the glue inlet and the glue outlet of the inner vacuum bag and the outer vacuum bag until the liquid resin completely infiltrates the fibers in S2, and then the liquid resin is cured ；
S4，所述液体树脂固化成型后，拆除第一可剥布、第二可剥布、隔离膜、导流网、内真空袋、透气毡和外真空袋，得到所述碳纳米管薄膜/复合材料闪电防护结构。S4: After the liquid resin is cured and formed, the first peelable cloth, the second peelable cloth, the isolation film, the guide net, the inner vacuum bag, the air felt, and the outer vacuum bag are removed to obtain the carbon nanotube film/composite Material lightning protection structure.
所述脱模剂为AXEL CX-500、PMR-EZ或其它同等功能牌号，在清理模具后涂覆，固化后辅助脱模。The mold release agent is AXEL CX-500, PMR-EZ or other equivalent functional brands, and is applied after cleaning the mold, and assists the mold release after curing.
所述S2中的铺放采用手工铺放或自动铺放，自动铺放采用自动铺带机或自动铺丝机。The laying in the S2 adopts manual laying or automatic laying, and the automatic laying adopts an automatic tape laying machine or an automatic silk laying machine.
S3中所述固化采用热压罐或固化炉进行固化。The curing described in S3 adopts an autoclave or a curing oven for curing.
S3中真空的真空度为-90KPAa以上。The vacuum degree of vacuum in S3 is above -90KPAa.
S3中固化的温度及固化时间随着不同树脂体系不同而有异，常用的航空树脂体系固化温度为180℃，固化时间为2h。The curing temperature and curing time in S3 vary with different resin systems. The curing temperature of the commonly used aviation resin system is 180°C and the curing time is 2h.
所述液体树脂灌入的量由最终复合材料的纤维含量倒推计算；树脂由进胶口进入，多余树脂由出胶口溢出。The amount of the liquid resin poured in is calculated backwards from the fiber content of the final composite material; the resin enters through the glue inlet, and the excess resin overflows from the glue outlet.
所述复合材料中，纤维的体积含量为55％左右，树脂和纤维的体积之和是100％。In the composite material, the volume content of the fiber is about 55%, and the sum of the volume of the resin and the fiber is 100%.
所述成型方法中，可剥布、隔离膜为辅助材料，保护辅助材料表面，导流网为液体成型工艺中的树脂导流介质，辅助树脂浸润干纤维预成型体；内真空袋用于提供所需真空环境，以吸入树脂；透气起到导气作用，时真空袋内各区域压力 均匀；外真空袋一方面在内真空袋破损的情况下防止漏气，用于保证真空；另一方面内真空袋不漏的情况下提供外在均匀压力，使复合材料各区域厚度方向压力相同，厚度均匀。In the molding method, the peelable cloth and the isolation film are auxiliary materials to protect the surface of the auxiliary materials, the diversion net is the resin diversion medium in the liquid molding process, and the auxiliary resin infiltrates the dry fiber preform; the inner vacuum bag is used to provide The vacuum environment is required to inhale the resin; the ventilation plays a role of air conduction, and the pressure of each area in the vacuum bag is even; on the one hand, the outer vacuum bag prevents air leakage when the inner vacuum bag is damaged, and is used to ensure the vacuum; on the other hand The internal vacuum bag provides uniform external pressure without leaking, so that the pressure in the thickness direction of each area of the composite material is the same, and the thickness is uniform.
实施例3Example 3
本实施例提供一种制备实施例1中的碳纳米管薄膜/复合材料闪电防护结构的成型方法，所述复合材料为预浸料时，采用热压罐制备得到所述碳纳米管薄膜/复合材料闪电防护结构；具体为：将碳纳米管薄膜、胶膜和预浸料依次铺放，置于热压罐中固化得到所述碳纳米管薄膜/复合材料闪电防护结构。This embodiment provides a method for preparing the carbon nanotube film/composite lightning protection structure in Example 1. When the composite material is a prepreg, the carbon nanotube film/composite is prepared by using a hot autoclave. Material lightning protection structure; specifically: the carbon nanotube film, the glue film and the prepreg are laid in sequence, and then placed in a hot autoclave for curing to obtain the carbon nanotube film/composite material lightning protection structure.
以上对本发明实施例所提供的一种碳纳米管薄膜/复合材料闪电防护结构及其成型方法进行了详细介绍。以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。In the foregoing, the carbon nanotube film/composite lightning protection structure and the forming method thereof provided by the embodiments of the present invention have been introduced in detail. The description of the above embodiments is only used to help understand the method and core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation and the scope of application. In summary, the content of this specification should not be construed as a limitation to the present invention.
如在说明书及权利要求书当中使用了某些词汇来指称特定组件。本领域技术人员应可理解，硬件制造商可能会用不同名词来称呼同一个组件。本说明书及权利要求书并不以名称的差异来作为区分组件的方式，而是以组件在功能上的差异来作为区分的准则。如在通篇说明书及权利要求书当中所提及的“包含”、“包括”为一开放式用语，故应解释成“包含/包括但不限定于”。“大致”是指在可接收的误差范围内，本领域技术人员能够在一定误差范围内解决所述技术问题，基本达到所述技术效果。说明书后续描述为实施本发明的较佳实施方式，然所述描述乃以说明本发明的一般原则为目的，并非用以限定本发明的范围。本发明的保护范围当视所附权利要求书所界定者为准。For example, certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that hardware manufacturers may use different terms to refer to the same component. This specification and claims do not use differences in names as a way of distinguishing components, but use differences in functions of components as a criterion for distinguishing. If "include" and "include" mentioned in the entire specification and claims are open-ended terms, they should be interpreted as "include/include but not limited to". "Approximately" means that within the acceptable error range, those skilled in the art can solve the technical problem within a certain error range, and basically achieve the technical effect. The following description of the specification is a preferred embodiment for implementing the present invention, but the description is for the purpose of explaining the general principles of the present invention, and is not intended to limit the scope of the present invention. The protection scope of the present invention shall be subject to those defined by the appended claims.
还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的商品或者***不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种商品或者***所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的商品或者***中还存在另外的相同要素。It should also be noted that the terms "include", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a commodity or system that includes a series of elements not only includes those elements, but also includes those elements that are not explicitly listed. Other elements of, or also include elements inherent to this commodity or system. If there are no more restrictions, the element defined by the sentence "including a..." does not exclude the existence of other identical elements in the commodity or system that includes the element.
应当理解，本文中使用的术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时 存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。It should be understood that the term "and/or" used in this text is only an association relationship describing the associated objects, indicating that there can be three types of relationships, for example, A and/or B can mean that A alone exists, and both A and A exist at the same time. B, there are three cases of B alone. In addition, the character "/" in this text generally indicates that the associated objects before and after are in an "or" relationship.
上述说明示出并描述了本发明的若干优选实施例，但如前所述，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述申请构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求书的保护范围内。The above description shows and describes several preferred embodiments of the present invention, but as mentioned above, it should be understood that the present invention is not limited to the form disclosed herein, and should not be regarded as the exclusion of other embodiments, but can be applied to various embodiments. Such other combinations, modifications, and environments can be modified through the above teachings or technology or knowledge in related fields within the scope of the application concept described herein. The modifications and changes made by those skilled in the art do not depart from the spirit and scope of the present invention, and should fall within the protection scope of the appended claims of the present invention.

Claims (10)

  1. 一种碳纳米管薄膜/复合材料闪电防护结构的成型方法，其特征在于，所述成型方法采用低成本液体成型一步法整体得到超轻碳纳米管薄膜/复合材料闪电防护结构。A method for forming a carbon nanotube film/composite lightning protection structure is characterized in that the molding method adopts a low-cost liquid molding one-step method to integrally obtain an ultralight carbon nanotube film/composite lightning protection structure.
  2. 根据权利要求1所述的成型方法，其特征在于，所述成型方法包括以下步骤：The molding method according to claim 1, wherein the molding method comprises the following steps:
    S1，选取液体成型工艺用工装，清理工装并涂脱模剂；S1, select tooling for liquid molding process, clean the tooling and apply release agent;
    S2，工装从下到上依次铺放第一可剥布、碳纳米管薄膜、胶膜、纤维、第二可剥布、隔离膜、导流网、内真空袋、透气毡和外真空袋；所述内真空袋和外真空外与所述工装接触处密封，采用密封胶密封；S2: Lay the first peelable cloth, the carbon nanotube film, the glue film, the fiber, the second peelable cloth, the isolation film, the deflector net, the inner vacuum bag, the air felt, and the outer vacuum bag in sequence from bottom to top on the tooling; The contact between the inner vacuum bag and the outer vacuum bag and the tooling is sealed, and sealed with a sealant;
    S3，在抽真空作用下，将液体树脂从所述内真空袋和外真空袋的进胶口导入、出胶口导出，直至所述液体树脂完全浸润S2中的纤维，再固化所述液体树脂；S3: Under the action of vacuuming, the liquid resin is introduced from the glue inlet and the glue outlet of the inner vacuum bag and the outer vacuum bag until the liquid resin completely infiltrates the fibers in S2, and then the liquid resin is cured ；
    S4，所述液体树脂固化成型后，拆除第一可剥布、第二可剥布、隔离膜、导流网、内真空袋、透气毡和外真空袋，得到所述碳纳米管薄膜/复合材料闪电防护结构。S4: After the liquid resin is cured and formed, the first peelable cloth, the second peelable cloth, the isolation film, the guide net, the inner vacuum bag, the air felt, and the outer vacuum bag are removed to obtain the carbon nanotube film/composite Material lightning protection structure.
  3. 根据权利要求2所述的成型方法，其特征在于，所述脱模剂为AXEL CX-500、PMR-EZ或其它型号的脱模剂，在清理工装后涂覆，固化后辅助脱模。The molding method according to claim 2, wherein the mold release agent is AXEL CX-500, PMR-EZ or other types of mold release agents, which are applied after cleaning the tooling and assisted demolding after curing.
  4. 根据权利要求2所述的成型方法，其特征在于，所述S2中的铺放采用手工铺放或自动铺放，自动铺放采用自动铺带机或自动铺丝机。The molding method according to claim 2, wherein the laying in S2 adopts manual laying or automatic laying, and the automatic laying adopts an automatic tape laying machine or an automatic silk laying machine.
  5. 根据权利要求2所述的成型方法，其特征在于，S3中所述固化采用热压罐或固化炉进行固化。The molding method according to claim 2, characterized in that the curing in S3 is carried out by using a hot autoclave or a curing furnace.
  6. 一种采用如权利要求1～5任一项所述的成型方法制备得到的碳纳米管薄膜/复合材料闪电防护结构，其特征在于，所述闪电防护结构包括：A carbon nanotube film/composite lightning protection structure prepared by the molding method according to any one of claims 1 to 5, wherein the lightning protection structure comprises:
    用作导电层的碳纳米管薄膜；Carbon nanotube film used as a conductive layer;
    复合材料，包括纤维和填充在纤维中的树脂；Composite materials, including fibers and resin filled in fibers;
    胶膜，用于对所述复合材料和碳纳米管薄膜之间的电绝缘；An adhesive film for electrical insulation between the composite material and the carbon nanotube film;
    所述碳纳米管薄膜、胶膜和复合材料依次设置。The carbon nanotube film, the glue film and the composite material are arranged in sequence.
  7. 根据权利要求6所述的碳纳米管薄膜/复合材料闪电防护结构，其特征在于，所述碳纳米管薄膜为连续高导电超轻碳纳米管薄膜。The carbon nanotube film/composite material lightning protection structure of claim 6, wherein the carbon nanotube film is a continuous high-conductivity ultra-light carbon nanotube film.
  8. 根据权利要求6所述的碳纳米管薄膜/复合材料闪电防护结构，其特征在 于，所述碳纳米管薄膜的厚度不小于15μm。The carbon nanotube film/composite material lightning protection structure according to claim 6, wherein the thickness of the carbon nanotube film is not less than 15 m.
  9. 根据权利要求6所述的碳纳米管薄膜/复合材料闪电防护结构，其特征在于，所述碳纳米管薄膜的面密度不大于10g/m 2。 The carbon nanotube film/composite material lightning protection structure according to claim 6, wherein the surface density of the carbon nanotube film is not greater than 10 g/m 2 .
  10. 根据权利要求6所述的碳纳米管薄膜/复合材料闪电防护结构，其特征在于，所述碳纳米管薄膜的电导率为10 4-10 6s/m。 The carbon nanotube film/composite material lightning protection structure according to claim 6, wherein the electrical conductivity of the carbon nanotube film is 10 4 -10 6 s/m.
PCT/CN2019/114633 2019-09-20 2019-10-31 Carbon nanotube thin film/composite material forming method and manufactured lightning protection structure WO2021051486A1 (en)

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